Process for the production of alkali metal-cellulose-silicates and their reaction products

ABSTRACT

Small particles of cellulose-containing plants, fine granular oxidated silicon compounds and an alkali metal hydroxide are mixed, then heated to 150° C. to 220° C. while agitating until the plant particles soften or melt, thereby producing an alkali metal cellulose silicate condensation product.

BACKGROUND OF THE INVENTION

This invention relates to a novel and economical process to break downparticles of cellulose-containing plants into smaller polymers andcompounds, and in the process, they react with the oxidated siliconcompounds which are highly reactive chemically and are soluble in waterand/or common organic solvents.

This process requires temperatures high enough to melt the solid alkalimetal hydroxide in order for it to react with the cellulose-containingplants and oxidated silicon compounds. It is not necessary to remove thelignin from wood in the process of this invention. When an organic orinorganic acid compound is added to the alkali metal-cellulose-silicatecondensation product, carbon dioxide is given off. This carbon dioxidemay be used to produce foamed products. The alkalimetal-cellulose-silicate condensation product is a dark brown, solidproduct which softens at about 150° C. and becomes a thick liquidbetween 150° C. to 200° C.

When wood is used as the cellulose-containing plant, the usuallignin-cellulose bond is not broken in most cases, but the molecules ofcellulose are broken down into smaller molecules and react with theoxidated silicon compounds to produce alkali metal-cellulose-silicatecondensation products. These condensation products are highly reactivechemically, especially with aldehydes, furan compounds, polyisocyanates,polyurethane prepolymers, polyisocyanate silicate prepolymers,isocyanates, ketones, vinyl acetate, acrylic acid monomers, allylhalides, polyfunctioning alkylating agents, monofunctional alkylatingagents, acrylic acid compounds with other vinyl monomers, epihalohydrinswith polyamines, sulfur, silicon halides, organic polyhalides andpolyamines, furfuryl alcohol, compounds which contain halogen atomscapable of being quaternized or R-SO₂ -groups, epoxide compounds,aldehydes and phenols, aldehydes and amino compounds, vinyl acetate withother vinyl monomers, halohydrins and mixtures thereof.

An aqueous solution of the alkali metal-cellulose-silicate condensationproduct may be used commercially to react with polyisocyanates,isocyanate-terminated polyurethane prepolymers, polyisocyanate silicateprepolymers and isocyanate-terminated polyurethane silicate prepolymers.The aqueous solution of the alkali metal-cellular-silicates may producenovel and useful products by being polymerized with aldehydes, furfurylalcohol, halohydrins, epihalohydrins and polyamines, ketones, organicepoxides, vinyl monomers, allyl halides, organic polyhalides, organichalides, organic acid sulfates, organic poly(acid sulphates), organicnitrates, organic polynitrates, organic acid phosphates, organicpoly(acid phosphates), organic bicarbonates, organic poly(bicarbonatecompounds containing radicals), organic compounds containing formateradicals, organic compounds containing poly(formate) radicals, organiccompounds containing acetate, propionate laurate, oleate, stearate,oxalate, acid malonate, acid tartrate, acid citrate radical and mixturesthereof, sulfur and mixtures thereof.

The water-soluble alkali metal-cellulose-silicate condensation productmay be precipitated by the addition of a salt-forming compound, such asan organic or inorganic acid. The water is filtered off. The watercontains 5% to 30% by weight of water-soluble cellulose-containing plantpolymers; these may be recovered by evaporating the water. Theprecipitated cellulose-silicate condensation product is in the form ofdark brown- to black-colored fine particles which are soluble in aceticacid, alcohols, dilute alkali hydroxide solutions and other organicsolvents.

The cellulose-silicate reaction product will react chemically withisocyanate compounds, polyisocyanate compounds, polythiocyanates,thiocyanates, polyurethane prepolymers, polyisocyanate silicateprepolymers, polyurethane silicate prepolymers, silicon halides,polycarboxyl acids and their corresponding anhydrides, organic epoxides,aldehydes, ketones, furfuryl alcohol, epihalohydrins and mixturesthereof.

At least 3 components are used to produce alkalimetal-cellulose-silicate condensation product such as:

Component A: Cellulose-containing plants;

Component B: Oxidated silicon compound;

Component C: Alkali metal hydroxide.

Component A

Any suitable cellulose-containing plant or the products ofcellulose-containing plants which contain cellulose may be used in thisinvention. The plant material is preferred to be in the form of smallparticles such as sawdust. In nature, cellulose is widely distributed.It is found in all plants, and they may be used in this process,preferably in a dry, small-particle form.

Suitable cellulose-containing plants include, but are not limited to,trees, e.g., spruce, pine, hemlock, fir, oak, ash, larch, birch, aspen,poplar, cedar, beech, maple, walnut, cypress, redwood, cherry, elm,chestnut, hickory, locust, sycamore, tulip, tupelo, butternut, apple,alder, magnolia, dogwood, catalpa, boxwood, crabwood, mahogany,greenheart, lancewood, letterwood, mora, prima vera, purpleheart,rosewood, teak, satinwood, mangrove, wattle, orange, lemon, logwood,fustic, osageorgane, sappanwood, Brazilwood, barwood, camwood,cottonwood, sandalwood, rubber, gutta, and mesquite; shrubs, e.g.,oleander, cypress, junipers, acanthus, pyracantha, lugustrum, lantana,bougainvilla, azalea, feijoa, ilex, fuchsia, hibiscus, datura, holly,hydrangea, jasmine, eucalyptus, cottoneaster, xylosma, rhododendron,castor bean, eugenia, euonymus, fatshedera, aralia, etc.; agriculturalplants, e.g., cotton, cotton stalks, corn stalks, corn cobs, wheatstraw, oat straw, rice straw, cane sugar (bagasse), soybean stalks,peanut plants, pea vines, sugar beet waste, sorghum stalks, tobaccostalks, maize stalks, barley straw, buckwheat straw, quinoa stalks,cassava, potato plants, legume vines and stalks, vegetable (inedibleportion), etc.; weeds, grasses, vines, kelp, flowers, algae and mixturesthereof. Wood fibers and cotton fibers are the preferredcellulose-containing materials. The waste products of agriculturalplants may be air-dried, then ground into small particles and used inthis invention. Commercial waste products containing cellulose, e.g.,paper, cotton clothes, bagasse wallboard, wood products, etc., may beused in this invention. Wood with the lignin removed (wood pulp) may beused in this invention. Cellulose-containing plants which have beenpartially decomposed, such as humus, peat and certain soft brown coalmay be used in this invention.

Other products of plants may be recovered in the process of thisinvention such as waxes, gums, oils, sugars, alcohols, agar, rosin,turpentine, resins, rubber latex, dyes, etc.

Component B

Any suitable oxidated silicon compound may be used in this invention.Suitable oxidated silicon compounds include silica, e.g., hydratedsilica, hydrated silica containing Si-H bonds (silicoformic acid),silica sol, silicic acid, silica, etc.; alkali metal silicates, e.g.,sodium silicate, potassium silicate, lithium silicate, etc., naturalsilicates with free silicic acid groups and mixtures thereof.

Silica is the preferred oxidated silicon compound.

Component C

Any suitable alkali metal hydroxide may be used in this invention.Suitable alkali metal hydroxides include sodium hydroxide, potassiumhydroxide and mixtures thereof. Sodium hydroxide is the preferred alkalimetal hydroxide.

The alkali metal-cellulose-silicate condensation product may be reactedwith inorganic acids, e.g., sulfuric acid, hydrochloric acid, nitricacid, phosphoric acid, sulphurous acid, hypophosphorous acid,fluorobaric acid, etc.; organic acid, e.g., acetic acid, propionic acid,glycolic acid, lactic acid, succinic acid, tartaric acid, oxalic acid,phthalic acid, trimellitic acid and the like; phosphinic acid,phosphonous acid, phosphonic acid, amidosulphonic acid, etc.; inorganichydrogen-containing salts e.g., sodium hydrogen sulphate, potassiumhydrogen sulphate, sodium dihydrogen phosphate, potassium dihydrogenphosphate and the like, to produce cellular solid cellulose-silicateproducts. Carbon dioxide is released in the reaction to produce aircells in the cellulosesilicate products. Further examples of acids maybe found in German Pat. No. 1,178,586 and in U.S. Pat. No. 3,480,592,and these acids may be used in this invention.

The acid compounds may also be used to react with the alkali metal atomsin the alkali metal-cellulose-silicate condensation product to produce asalt and also release CO₂ which expands the cellulose-silicate and thecellulose-silicate reaction products into cellular solid products. Theacid compounds may also be used as a catalyst in the reactions toproduce foamed aminoplast-cellulose-silicate solid products, foamedphenoplast-cellulose-silicate solid products,aldehyde-cellulose-silicate cellular solid products,polyurethane-cellulose-silicate cellular solid products andcellulose-silicate cellular products.

Any suitable aldehyde may be used in this invention, such asformaldehyde, acetaldehyde, butyl aldehyde, chloral, acrolein, furfural,benzaldehyde, crotonaldehyde, propionaldehyde, pentanals, hexanals,heptanals, octanals and their substitution products, semi-acetals andfull acetals, paraformaldehyde and mixtures thereof. Compoundscontaining active aldehyde groups such as hexamethylene tetramine mayalso be used to produce aldehyde-cellulose-silicate cellular solid orsolid reaction products.

Any suitable amino compound may be used in this invention to produceaminoplast-cellulose-silicate reaction products such as urea, thiourea,alkyl-substituted thiourea, alkyl-substituted ureas, melamine, aniline,quanidine, saccharin, dicyandiamide, benzene sulfonamides, toluenesulfonamide, aliphatic and aromatic polyamines and mixtures thereof.Urea is the preferred amino compound, and formaldehyde is the preferredaldehyde when used with an amino compound.

Any suitable phenol compound may be used in this invention to producephenoplast-cellulose-silicate cellular solid or solid reaction productssuch as phenol, p-cresol, o-cresol, m-cresol, cresylic acid, xylenols,resorcinol, chashew nut shell liquid, anacordol, p-tert-butyl phenol,Bisphenol A, creosote oil, 2,6-dimethylphenol and mixtures thereof.Phenol is the preferred phenol compound and formaldehyde is thepreferred aldehyde when used with a phenol compound.

Any suitable mixture of the amino compounds and phenol compounds with analdehyde may be used in this invention to produceaminoplast-phenoplast-cellulose-silicate solid or cellular solidproducts.

Any suitable organic polyisocyanate may be used according to theinvention, including aliphatic, cycloaliphatic, araliphatic, aromaticand heterocyclic polyisocyanates. Suitable polyisocyanates which may beemployed in the process of the invention are exemplified by the organicdiisocyanates which are compounds of the general formula:

    O═C═N--R--N═C═O

where R is a divalent organic radical such as an alkylene, aralkylene orarylene radical. Such suitable radicals may contain, for example, 2 to20 carbon atoms. Examples of such diisocyanates are:

tolylene diisocyanate

p,p'-diphenylmethane diisocyanate (sic)

phenylene diisocyanate

m-xylylene diisocyanate

chlorophenylene diisocyanate

benzidene diisocyanate

naphthylene diisocyanate

decamethylene diisocyanate

hexamethylene diisocyanate

pentamethylene diisocyanate

tetramethylene diisocyanate

thiodipropyl diisocyanate

propylene diisocyanate

ethylene diisocyanate

Other polyisocyanates, polyisothiocyanates and their derivatives may beequally employed. Fatty diisocyanates are also suitable and have thegeneral formula ##STR1## where x+y totals 6 to 22 and z is 0 to 2, e.g.,isocyanastearyl isocyanate.

It is generally preferred to use commercially readily availablepolyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and anymixtures of these isomers ("TDI"), polyphenyl-polymethyleneisocyanatesobtained by aniline-formaldehyde condensation followed by phosgenation("crude MDI"), and modified polyisocyanate containing carbodiimidegroups, allophanate groups, isocyanurate groups, urea groups, imidegroups, amide groups or biuret groups, said modified polyisocyanatesprepared by modifying organic polyisocyanates thermally or catalyticallyby air, water, urethanes, alcohols, amides, amines, carboxylic acids, orcarboxylic acid anhydrides. Phosgenation products of condensates ofaniline or anilines alkylsubstituted on the nucleus, with aldehydes orketones may be used in this invention. Solutions of distillationresidues accumulating during the production of tolylene diisocyanates,diphenyl methane diisocyanate, or hexamethylene diisocyanate, inmonomeric polyisocyanates or in organic solvents or mixtures thereof maybe used in this invention. Organic triisocyanates such astriphenylmethane triisocyanate may be used in this invention.Cycloaliphatic polyisocyanates, e.g., cyclohexylene-1,2; cyclohexylene1,4-; and methylene-bis-(cyclohexyl-4,4') diisocyanate may be used inthis invention. Suitable polyisocyanates which may be used according tothe invention are described, e.g., by W. Siefkin in Justus LiebigsAnnalen der Chemie, 562, pages 75 to 136. Inorganic polyisocyanates arealso suitable according to the invention.

Organic polyhydroxyl compounds (polyols) may be used in this inventionwith polyisocyanates or may be first reacted with a polyisocyanate toproduce isocyanate-terminated polyurethaneprepolymers and then also usedin this invention.

Reaction products of from 50 to 99 mols of aromatic diisocyanates withfrom 1 to 50 mols of conventional organic compounds with a molecularweight of, generally, from about 200 to about 10,000, which contain atleast two hydrogen atoms capable of reacting with isocyanates, may alsobe used. While compounds which contain amino groups, thiol groups,carboxyl groups or silicate groups may be used, it is preferred to useorganic polyhydroxyl compounds, in particular, compounds which containfrom 2 to 8 hydroxyl groups, especially those with a molecular weight offrom about 800 to about 10,000 and preferably from about 1,000 to about6,000, e.g., polyesters, polyethers, polythioethers, polyacetals,polycarbonates or polyester amides containing at least 2, generally from2 to 8, but preferably dihydric alcohols, with the optional addition oftrihydric alcohols, and polybasic, preferably dibasic, carboxylic acids.Instead of the free polycarboxylic acids, the correspondingpolycarboxylic acid anhydrides or corresponding polycarboxylic acidesters of lower alcohols or their mixtures may be used for preparing thepolyesters. The polycarboxylic acid may be aliphatic, cycloaliphatic,aromatic and/or heterocyclic and may be substituted, e.g., with halogenatoms and may be unsaturated; examples include: succinic acid, adipicacid, sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalicacid anhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, endomethylene tetrahydrophthalic acid anhydride,glutaric acid anhydride, fumaric acid, maleic acid, maleic acidanhydride, dimeric and trimeric fatty acid such as oleic acid,optionally mixed with monomeric fatty acids, dimethylterephthalate andbis-glycol terephthalate. Any suitable polyhydric alcohol may be usedsuch as, for example, ethylene glycol; propylene-1,2- and -1,3-glycol;butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol;neopentyl glycol,cyclohexanedimethanol-(1,4-bis-hydroxymethylcyclohexane);2-methylpropane-1,3-diol; glycerol; trimethylol propane;hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane;pentaerythritol; quinitol; mannitol and sorbitol; methylgrycoside;diethylene glycol; triethylene glycol; tetraethylene glycol;polyethylene glycols; dipropylene glycol; polypropylene glycols;dibutylene glycol and polybutylene glycols. The polyesters may alsocontain a proportion of carboxyl end groups. Polyesters of lactones,such as ε-caprolactone, or hydroxycarboxylic acid such asω-hydroxycaproic acid, may also be used.

The polyethers with at least 2, generally from 2 to 8 and preferably 2or 3, hydroxyl groups used according to the invention are known and maybe prepared, e.g., by the polymerization of epoxides, e.g., ethyleneoxide propylene oxide, butylene oxide, tetrahydrofurane oxide, styreneoxide or epichlorohydrin, each with itself, e.g., in the presence ofBF₃, or by addition of these epoxides, optionally as mixtures orsuccessively, to starting components which contain reactive hydrogenatoms such as alcohols or amines, e.g., water, ethylene glycol;propylene-1,3- or 1,2-glycol; trimethylol propane;4,4-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine orethylenediamine; sucrose polyethers such as those described, e.g., inGerman Auslegeschriften Nos. 1,176,358 and 1,064,938 may also be usedaccording to the invention. It is frequently preferred to use polyetherswhich contain predominantly primary OH groups (up to 90% by weight,based on the total OH groups contained in the polyether). Polyethersmodified with vinyl polymers such as those which may be obtained bypolymerizing styrene or acrylonitrites in the presence of polyethers,(U.S. Pat. Nos. 3,383,351; 3,304,273; 3,523,093 and 3,110,695; andGerman Pat. No. 1,152,536) and polybutadienes which contain OH groupsare also suitable.

By "polythioethers" are meant, in particular, the condensation productsof thiodiglycol with itself and/or with other glycols, dicarboxylicacids, formaldehyde, aminocarboxylic acids or amino alcohols. Theproducts obtained are polythio-mixed ethers or polythioether esteramides, depending on the co-component.

The polyacetals used may be, for example, the compounds which may beobtained from glycols, 4,4'-dihydroxydiphenylmethylmethane, hexanediol,and formaldehyde. Polyacetals suitable for the invention may also beprepared by the polymerization of cyclic acetals.

The polycarbonates with hydroxyl groups used may be of the kind, e.g.,which may be prepared by reaction diols, e.g., propane-1,3-diol;butane-1,4-diol; and/or hexane-1,6-diol or diethylene glycol,triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g.,diphenylcarbonates or phosgene.

The polyester amides and polyamides include e.g., the predominantlylinear condensates obtained from polyvalent saturated and unsaturatedcarboxylic acids or their anhydrides and polyvalent saturated andunsaturated amino alcohols, diamines, polyamines and mixtures thereof.

Polyhydroxyl compounds which contain urethane or urea groups, modifiedor unmodified natural polyols, e.g., castor oil, carbohydrates andstarches, may also be used. Additional products of alkylene oxides withphenol formaldehyde resins or with ureaformaldehyde resins are alsosuitable for the purpose of the invention.

Organic hydroxyl silicate compound as produced in U.S. Pat. No.4,139,549 may also be used in this invention.

Examples of these compounds which are to be used according to theinvention have been described in High Polymers, Volume XVI,"Polyurethanes, Chemistry and Technology", published by Saunders-FrischInterscience Publishers, New York, London, Volume I, 1962, pages 32 to42 and pages 44 to 54, and Volume II, 1964, pages 5 and 6 and pages 198and 199; and in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen,Carl-Hanser-Verlag, Munich, 1966, on pages 45 to 71.

If the polyisocyanates or the prepolymer which contains NCO groups havea viscosity above 2000 cP at 25° C., it may be advantageous to reducethe viscosity thereof by mixing it with a low-viscosity organicpolyisocyanate and/or an inert blowing agent or solvent.

Inorganic polyisocyanates and isocyanate-terminated polyurethanesilicate prepolymers may also be used in this invention.

When an aqueous solution of alkali metal cellulose silicate is beingused to react with, or as a curing agent for, polyisocyanates, and incertain cases where the alkali metal cellulose silicate is reacting withpolyisocyanates, it is advantageous to use activators (catalysts) suchas tertiary amines, e.g., triethylamine, tributylamine, N-methylmorpholine, N-ethyl morpholine, tetramethylenediamine,pentamethyldiethylenetriamine, triethanolamine, triisopropanolamine,organo-metallic compound, e.g., tin acetate, tin oxtoate, tin ethylhexoate, dibutyl tin diacetate, dibutyl tin dilaurate and mixturesthereof.

Other examples of catalysts which may be used according to the inventionand details of their action are described in Kunststoff-Handbuch, VolumeVII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich, 1966,on pages 96 and 102. Silaamines are suitable catalysts, e.g.,2,2,4-trimethyl-2-silamorpholine or 1,3-diethyl aminoethyltetramethyldisiloxane. Suitable catalysts are also tetraalkyl ammonium hydroxides,alkali phenolates, alkali metal hydroxides, alkali alcoholates andhexahydrotriazines.

Suitable flame-resistant compounds may be used in the products of thisinvention such as those which contain halogen or phosphorus, e.g.,tributylphosphate; tris(2,3-dichloropropyl)-phosphate;polyoxypropylenechloromethylphosphonate; cresyldiphenylphosphate;tricresylphosphate; tris-(beta-chloroethyl)-phosphate;tris-(2,3-dichloropropyl)-phosphate; triphenyl-phosphate; ammoniumphosphate; perchlorinated diphenyl phosphate; perchlorinated terephenylphosphate; hexabromocyclodecane; tribromophenol; dibromopropyldiene,hexabromobenzene; octabromodiphenylether; pentabromotoluol;poly-tribromostyrol; tris-(bromocresyl)-phosphate; tetrabromobis-phenolA; tetrabromophthalic acid anhydride; octabromodiphenyl phosphate;tri-(dibromopropyl)-phosphate; calcium hydrogen phosphate; sodium orpotassium dihydrogen phosphate; disodium or dipotassium hydrogenphosphate; ammonium chloride; phosphoric acid; polyvinylchloridetetomers chloroparaffins as well as further phosphorus- and/orhalogen-containing flame-resistant compounds as they are described in"Kunststoff-Handbuch", Volume VII, Munich, 1966, pages 110 and 111,which are incorporated herein by reference. The organichalogen-containing components are, however, preferred in thepolyurethane-cellulose-silicate products. In the production ofaldehyde-cellulose-silicate, aminoplast-cellulose-silicate,phenoplast-cellulose-silicate cellular products, and phosphoric acid maybe used to react with the alkali metal atoms, thereby producing analkali metal hydrogen phosphate which may be used as the flame-resistantcompound.

DETAILED DESCRIPTION OF THE INVENTION

The preferred process to produce the alkali metal-cellulose-silicatecondensation product is to mix about 3 parts by weight of air-dried fineparticles of a plant, 1, to 2 parts by weight of an oxidated siliconcompound and 2 to 5 parts by weight of an alkali metal hydroxidecompound, then to heat the mixture at ambient pressure and 150° C. to220° C. for 5 to 60 minutes, thereby producing an alkalimetal-cellulose-silicate condensation product.

The alkali metal-cellulose-silicate polymer softens or melts into athick liquid at 150° C. to 220° C. and when it cools, it forms adark-brown solid mass. The mass is easily broken up into fine particlesand is soluble in organic solvent, e.g., alcohols, polyols,epichlorohydrin, chlorohydrin, etc., and/or water.

The alkali metal-cellulose-silicate condensation product may beneutralized with an acid compound to a pH of about 7 to produce a foamedcellulose-silicate product by the production of CO₂ when the acid reactswith the alkali metal atoms to form a salt. The foamedcellulose-silicate product may be optionally washed to remove the salt,then dried, and may be utilized for thermal- and sound-insulationmaterial in construction of buildings, cars, boats and airplanes. Thefoamed cellulose-silicate may also be reacted with polyurethane and/orisocyanate-terminated polyurethane prepolymers.

In an additional preferred process, about 2 parts by weight of thealkali metal-cellulose-silicate condensation product produced by theprocess of the invention are mixed with 1 to 5 parts by weight of analdehyde, then agitated at ambient temperature and pressure for 10 to 60minutes, thereby producing an aldehyde-alkali metal-cellulose-silicatecopolymer. The aldehyde-alkali metal-cellulose-silicate copolymer isthen reacted with an acid compound until the pH is 6 to 7, therebyproducing a foamed aldehyde-cellulose-silicate copolymer. The salt isremoved by washing and filtering.

In an additional preferred process, about 2 parts by weight of thealkali metal-cellulose-silicate condensation product produced by theinvention are mixed with 1 to 5 parts by weight of an amino compound and0.5 to 5 mols of an aldehyde for each mol of the amino compound, thenagitated at a temperature and pressure between ambient temperature and100° C. for 10 minutes to 12 hours, thereby producing anaminoplast-alkali metal-cellulose-silicate resin; then an acid compoundis added until the pH is 5 to 7, while agitating until the mixturebegins to expand, thereby producing a cellular solidaminoplast-cellular-silicate product.

In an additional preferred process, about 2 parts by weight of thealkali metal-cellulose-silicate condensation product produced by theprocess of this invention are mixed with 1 to 5 parts by weight of aphenol compound and 1 to 5 mols of an aldehyde per mol of the phenolcompound, then agitated at a temperature from ambient to 100° C. for 10minutes to 12 hours, thereby producing a phenoplast-alkalimetal-cellulose-silicate resinous product; then an acid compound isadded until the pH is 5 to 7 while agitating for a few seconds until themixture begins to expand, thereby producing a cellular solidphenoplast-cellulose-silicate product.

The processes to produce cellular solid aminoplast-cellulose-silicateproducts and phenoplast-cellulose-silicate cellular solid products maybe combined to produce cellular solidphenoplast-aminoplast-cellulose-silicate products.

In an additional preferred process, 1 to 4, parts by weight of thealkali metal-cellulose-silicate condensation product produced by theprocess of this invention and about 3 parts by weight of anisocyanate-terminated polyurethane prepolymer are rapidly and thoroughlymixed at ambient temperature and pressure, and in a few seconds to about120 minutes, the mixture expands 3 to 12 times its original volume toproduce a cellular solid polyurethane-cellulose-silicate product.

In an additional preferred process, one part by weight of an aqueoussolution containing 20% to 60% by weight of the alkalimetal-cellulose-silicate product produced by the process of thisinvention is mixed at ambient temperature and pressure with 1 to 10parts by weight of an organic polyisocyanate or polyisothiocyanate andthe mixture is optionally heated up to 100° C.; then in a few seconds to120 minutes, the reaction is complete, thereby producing apolyisocyanate-cellulose-silicate cellular solid or solid product.

In an additional preferred process, about 10 parts by weight of anaqueous solution containing 20% to 60% by weight of the alkalimetal-cellulose-silicate condensation product as produced by the processof this invention are mixed, at ambient pressure and temperature to 100°C., with 10 to 100 parts by weight of an isocyanate-terminatedpolyurethane prepolymer and optionally up to 0.01 part by weight of anamine catalyst; then in a few seconds to 120 minutes, the reaction iscomplete, thereby producing a polyurethane-cellulose-silicate cellularor solid product.

In an additional preferred process, 1 to 3 parts by weight of the alkalimetal-cellulose-silicate condensation product as produced by the processof this invention, 1 to 3 parts by weight of a polyol and 3 parts byweight of an organic polyisocyanate or polyisothiocyanate are rapidlymixed at ambient temperature and pressure; then in a few seconds to 120minutes, the reaction is complete, thereby producing apolyurethane-cellulose-silicate cellular solid or solid product.

In an additional preferred process, 2 parts by weight of the alkalimetal-cellulose-silicate condensation product as produced by the processof this invention are mixed with 1 to 4 parts by weight of an organicpolyisocyanate, then agitated for 10 to 60 minutes at a temperaturebetween 20° C. to 70° C., thereby producing a polyisocyanate-alkalimetal-cellulose-silicate prepolymer; then 10% to 100% by weight of acuring agent, based on the weight of the prepolymer, is added to theprepolymer while agitating at 20° C. to 80° C. for 5 to 20 minutes,thereby producing a cellular solid or solidpolyisocyanate-cellulose-silicate product.

In an additional preferred process, 1 to 3 parts by weight of the alkalimetal cellulose produced by the process of this invention, 1 to 3 partsby weight of a polyol (polyhydroxyl compound) and 1 to 3 parts by weightof an organic polyisocyanate or polyisothiocyanate are rapidly andthoroughly mixed at ambient temperature and pressure, and in a fewseconds to 5 minutes, the mixture begins to expand, expanding 3 to 12times its original volume, thereby producing a tough cellular solidpolyurethane-cellulose-silicate product.

When the alkali metal-cellulose-silicate produced by this invention isreacted with an acid compound, CO₂ is given off, and a foamedcellulose-silicate product is produced. In cases where inadequate CO₂ isproduced to form adequately expanded cellular solid cellulose-silicateproducts, a blowing agent may be used. The blowing agent may be added tothe alkali cellulose-silicate condensation product or to an aqueoussolution of the condensation product before the acid compound is added.The blowing agent may be also added with the acid compound. The chemicalreaction between the acid compound and the alkali metal atoms willusually produce enough heat to evaporate or expand the blowing agent; ifnecessary, an external source of heat may be used.

Readily volatile blowing agents, e.g., dichlorodifluoromethane,trichlorofluoromethane, butane, isobutylene, vinyl chloride, etc., maybe used to produce cellular solid products in this invention. Inaddition, the liquid reaction mixtures can be expanded into a foam bythe introduction of gases, optionally under pressure, such as air, CF₄,noble gases and H₂ O₂, the resulting foam being introduced into therequired mold and hardened therein. The resultant foam may optionallycontain foam stabilizers such as surfactants, foam formers, emulsifiersand, if desired, organic or inorganic fillers or diluents may initiallybe converted by blowing gas into a foam, and the resulting foam maysubsequently be mixed in a mixer with the other components, theresulting mixture being allowed to harden. Instead of blowing agents, itis also possible to use inorganic or organic, finely-divided hollowbodies such as expanded hollow beads of glass, plastic, straw, expandedclay, and the like, for producing foams.

The foams obtainable in this way can be used in either their dry ortheir moist form, if desired, after a compacting or tempering process,optionally carried out under pressure, as insulating materials, cavityfillings, packaging materials, building materials, etc. They can also beused in the form of sandwich elements, for example, with metal-coveringlayers in house, vehicle and aircraft construction.

It is also possible to introduce into the foaming reaction mixtures,providing they are still free-flowing, organic and/or inorganic foamableor already foamed particles such as, for example, expanded clay,expanded glass, wood, popcorn, cork, hollow beads of plastics such asvinyl chloride polymers, polyethylene, styrene polymers or foamparticles thereof or even, for example, polysulphone, polyepoxide,polyurethane, phenoplasts, aminoplasts, polyamide polymers, phenoplastsilicates, aminoplast silicates, epoxy silicate polymers, polyisocyanatepolymers, polyurethane silicate polymers or their reaction mixtures; thefoaming mixture may be allowed to foam through interstitial spacedparticles in packed volumes of these particles and, in this way,insulating materials can be produced. Combinations of expanded clay,glass or slate are especially preferred with the reaction mixture,according to the invention.

It is also possible to introduce into the foaming reaction mixtures,providing they are still free-flowing at a predetermined temperature, ablowing agent which is capable of evaporation or of gas formation atthis temperature, such as, for example, a halogenated hydrocarbon. Theinitial liquid mixture formed can be used not only for producing uniformfoams or non-uniform foams containing foamed or unfoamed fillers, but itcan also be used to foam through any given webs, woven fabrics,lattices, structural elements or other permeable structures of foamedmaterials, resulting in the formation of composite foams with specialproperties, for example, favorable flame behavior, which may optionallybe directly used as structural elements in the building, furniture,vehicle and aircraft industries.

The cellular solid products (foams) according to the invention can beadded to soil in the form of crumbs, optionally in admixtures withfertilizers and plant-protection agents, in order to improve itsagrarian consistency.

Since the hardened foams obtained by the process according to theinvention can show considerable porosity after drying, they are suitablefor use as drying agents because they can absorb water; however, theycan also be charged with active substances or used as catalyst supportsor as filters and absorbents.

On the other hand, the foams can be subsequently lacquered, metallized,coated, laminated, galvanized, subjected to vapor deposition, bonded orflocked in either their moist or their dry form or in impregnated form.The moldings can be further processed in their moist or their driedform, for example, by sawing, milling, drilling, planing, polishing andother machining techniques. The optionally filled moldings can befurther modified in their properties by thermal after-treatment,oxidation processes, hot-pressing, sintering processes or surfacemelting or other consolidation processes. Suitable mold materialsinclude inorganic and/or organic foamed or unfoamed materials such asmetals, for example, iron, nickel, fine steel, lacquered or, forexample, teflon-coated aluminum, porcelain, glass, wood, plastics suchas PVC, polyethylene, epoxide resins, ABS, polycarbonate, etc.

Fillers in the form of particulate or powdered materials can beadditionally incorporated into the liquid mixtures of the foamablereactants for a number of applications.

Suitable fillers include solid inorganic or organic substances, forexample, in the form of powders, granulate, wire, fibers, dumb bells,crystallites, spirals, rods, beads, hollow beads, foam particles, webs,pieces of woven fabric, knit fabrics, ribbons, pieces of film, etc.;pieces of dolomite, chalk, alumina, asbestos, basic silicas, sand,talcum, iron oxide, aluminum oxide and oxide hydrate, zeolites, calciumsilicates, basalt wool or powder, glass fibers, C-fibers, graphite,carbon black; Al-, Fe-, Cu-, Ag-powder; molybdenum sulphite, steel wool,bronze or copper cloth, silicon powder, expanded clay particles, hollowglass beads, glass powder, lava and pumice particles, wood chips,sawdust, cork, cotton, straw, jute, sisal, hemp, flax, rayon, popcorn,coke, particles of filled or unfilled, foamed or unfoamed, stretched orunstretched, organic polymers including plastics and rubber waste. Ofthe number of suitable organic polymers, the following, which can bepresent, for example, in the form of powders, granulate, foam particles,beads, hollow beads, foamable or unfoamed particles, fibers, ribbons,woven fabrics, webs, etc., are mentioned purely by way of examples:polystyrene, polyethylene, polypropylene, polyacrylonitrile,polybutadiene, polyisoprene, polytetrafluoroethylene, aliphatic andaromatic polyesters, melamine-urea or phenol resins, polyacetal resins,polyepoxides, polyhydantoins, polyurea, polyethers, polyurethanes,polyimides, polyamides, polysulphones, polycarbonates and, of course,any copolymers as well. Inorganic fillers are preferred.

Generally, the composite materials according to the invention can befilled with considerable quantities of fillers without losing theirvaluable property spectrum. The amount of fillers can exceed the amountof the reactants. In special cases, the foamed products of the presentinvention act as a binder for such fillers.

Basically, the production of the cellular solid products according tothe invention is carried out by mixing the reactants in one or morestages in a continuously- or intermittently-operating mixing apparatusand by then allowing the resulting mixture to foam and solidify, usuallyoutside the mixing apparatus in molds or on suitable materials. Thereaction temperature required for this, which may be from 0° C. to 200°C., and preferably from 20° C. to 160° C., may be achieved either byheating one or more of the reactants before the mixing process or byheating the mixing apparatus itself or, alternatively, by heating thereaction mixture after the components have been mixed. Combinations ofthese or other methods of adjusting the reaction temperature may, ofcourse, also be employed. In most cases, sufficient heat is evolvedduring the reaction to enable the reaction temperature to rise to valuesabove 50° C. after the reaction or foaming has begun.

In particular, however, the process according to the invention issuitable for in situ foaming on the building site. Any hollow formsobtained by means of shuttering in the conventional way may be filled upand used for foaming in this way.

The alkali metal-cellulose silicate condensation product as produced inthis invention may be pre-reacted with an aldehyde, then foamed by theaddition of an acid compound. The foamed particles may be dried and usedas insulation material by pouring a layer of the particles betweenrafters and studs in houses, buildings, etc., optionally containingflame-retardant agents.

The alkali metal-cellulose-silicate condensation product as produced inthis invention may be pre-reacted with an aldehyde, then foamed by theaddition of an acid compound. The foamed particles may be dried and usedas insulation material by pouring a layer of the particles betweenrafters and studs in houses, buildings, etc.

The alkali metal-cellulose-silicate as produced in this invention may bepre-reacted with an amino compound and an aldehyde to produce a liquidamino-aldehyde-alkali metal-cellulose-silicate condensation product,then be placed in a mixing chamber, optionally adding a blowing agent,emulsifier, foam stabilizer, filler, coloring agents, flame-retardantand other additives, then be rapidly mixed with and acid compound untilthe pH is 5 to 6.5 and then be pumped or blown by compressed air into amold such as a wall, ceiling, etc., while expanding, thereby producing acellular solid product, useful for sound and thermal insulation. Thefoaming components may also be pumped into a large mold to expand andharden into a cellular solid product. The cellular solid product may besawed into slats and used for insulation in houses, boats, vehicles,airplanes, etc. The cellular product may also be chopped by a suitablemachine into particles and poured or blown into places such as ceilings,walls, etc., and be used for thermal and sound insulation. The cellularproduct may also be used as a molding powder and molded into usefulproducts by heat and pressure in a mold.

The alkali metal-cellulose-silicate condensation product as produced inthis invention may be pre-reacted with a phenol compound and an aldehydeto produce a liquid condensation product. This liquid condensationproduct may be foamed by the addition of an acid compound in the samemanner as the amino-aldehyde-cellulose-silicate condensation product andmay be used for the same purposes, sound and thermal insulation. Thephenol-aldehyde-cellulose-silicate condensation product may be used as amolding powder, and in the production of paints, varnishes, adhesives,etc. The liquid phenol-aldehyde-alkali metal-cellulose-silicatecondensation product may be poured into a mold, then heated for 1 to 6hours at 60° C. to 90° C., thereby producing a tough, solid, usefulproduct.

The alkali metal-cellulose-silicate condensation product as produced inthis invention may be pre-reacted with a phenol compound, an aminocompound and an aldehyde compound so as to produce a liquid resin. Thisliquid resin may be poured into a mold, then heated to 70° C. to 100° C.for 1 to 6 hours, thereby producing a tough, solid, useful product. Thisliquid resin may also be foamed on the job by adding the liquid resinand an acid compound (catalyst) simultaneously to a mixing chamber, thenrapidly pumping or using air pressure to transfer the foaming mixtureinto a mold such as walls, ceilings, etc., where it rapidly sets withina few seconds to several minutes into a tough, rigid, somewhat elastic,cellular solid product, optionally containing a blowing agent,emulsifier, foam stabilizer, filler, flame-retardant agents and otheradditives. The product has good sound- and thermal-insulation qualities,good flame-retardant properties and good dimentional stability. Thephenoplast-aminoplast-cellulose-silicate resins may be used as moldingpowder and be molded by heat and pressure into useful objects. Thephenoplast-aminoplast-cellulose-silicate resins may be foamed into largeslabs, then sawed into various sizes and thicknesses or broken intosmall particles and used for thermal and sound insulation in houses,buildings, vehicles and aircrafts; these large slabs of foam may besawed into various thicknesses and widths, then a moisture barrier suchas aluminum foil may be applied by the use of an adhesive to produce aninsulation material that has excellent flame-resistant properties, goodstrength and excellent thermal and sound insulation qualities.

The process according to the invention to produce thepolyisocyanate-cellulose-silicate foam andpolyurethane-cellulose-silicate foam is particularly suitable, however,for in situ foaming on the building site. Any hollow molds normallyproduced by shuttering in forms can be used for casting and foaming. Thereaction mixture, optionally containing a blowing agent, emulsifier,foam stabilizer, filler, flame-retardant agent, diluents, dodorants,coloring agents and other agents, produced by adding the componentssimultaneously to a mixing apparatus, is immediately pumped or sprayedby compressed air into a mold, e.g., walls, ceilings, cold or heatedrelief molds, solid molds, hollow molds, etc., where it may be left toharden. The foaming reaction mixture may also be forced, cast orinjection molded into cold or heated molds, then hardened, optionallyunder pressure and at room temperature or at temperatures up to 200° C.,optionally using a centrifugal casting process. At this stagereinforcing elements in the form of inorganic and/or organic or metalwires, fibers, non-woven webs, foams, fabrics, supporting structures,etc., may be incorporated in the foaming mixtures. This may be achieved,for example, by the fibrous-web-impregnation process or by processes inwhich the reaction mixtures and reinforcing fibers are applied togetherto the mold, for example, by means of a spray apparatus. The moldedproducts obtained in this way may be used as building elements, e.g., inthe form of optionally foamed sandwich elements which may besubsequently laminated with metal, glass, plastics, etc. The firecharacteristics of the material are good, but are improved by theaddition of flame-retardant agents. On the other hand, the products maybe used as hollow bodies, e.g., as containers for goods which arerequired to be kept moist or cool, or the hollow bodies may be used asfilter materials or exchanges, as catalyst carriers or as carriers ofother active substances, as decoration elements, shock-resistantpackaging, furniture components and cavity fillings. They may also beused in the production of molds for metal casting and in model building.The cellular products may also be produced by pouring the componentsinto a mold, then mixing well, after which the mixture expands, thenhardens in the mold. The mold may be in the form of a large slab so thatit can be cut into various sizes, shapes and thicknessess as desired.The reaction mixtures may also be foamed up and hardened while in theform of droplets or may be dispersed, e.g., in petroleum hydrocarbons orwhile they are under condition of free fall. The foamed productsproduced by these methods may also be added in a crumbly form to soil,optionally with the addition of fertilizers and plant-protective agentsso as to improve the agricultural consistency of the soil. Foams whichhave a high water content may be used as substrates for the propagationof seedlings, shoots and plants or for cut flowers. The mixtures may besprayed on terrain which is impassible or too loose, such as dunes ormarshes, to strengthen such terrain so that it will be firm enough towalk on within a short time, and will be protected against erosion. Thefoaming mixtures may also be used underground in caves, mines, tunnels,etc., by spraying the foaming mixture onto wire mesh, fiberglass cloth,woven fabrics or directly on the walls, to produce protective layers toprevent cave-ins.

It is also possible to introduce into the foaming reaction mixtures,providing they are still free-flowing, inorganic and/or organic foamableor already foamed particles such as expanded clay, expanded glass, wood,popcorn, cork, hollow beads of plastics, for example, vinyl chloridepolymers, polyethylene, styrene polymers or foam particles thereof oreven, for example, polysulphone, polyepoxides, polyurethane,ureaformaldehyde, phenol formaldehyde, polyimide polymers, or thereaction mixtures may be allowed to foam through interstitial space inpacked volumes of these particles, and in this way to produce insulatingmaterials which are distinguished by excellent flame behavior.Combinations of expanded clay, glass, or slate with the reactionmixtures, according to the invention, are especially preferred.

Most of these polyisocyanate-cellulose-silicate andpolyurethane-cellulose-silicate cellular solid products are soluble incertain organic solvents and may be utlized as paints, varnishes,adhesives, fillers, caulking materials, etc.

The object of the present invention is to provide a novel process toproduce alkali metal-cellulose-silicate polymers fromcellulose-containing plants, alkali metal hydroxides and oxidatedsilicon compounds. Another object is to produce novel alkalimetal-cellulose-silicate condensation products which are highly reactiveand are water-soluble. Still another object is to produce novel alkalimetal-cellulose-silicate which will produce a gas, CO₂, when reactedwith an acid compound, thereby producing a foamed cellulose-silicatefoamed product. Another object is to produce novel solidcellulose-silicate condensation products. Still another object is toproduce alkali metal-cellulose-silicate condensation product which willreact chemically with aldehydes to produce novelaldehyde-cellulose-silicate solid or celluar solid products. Anotherobject is to produce novel alkali metal-cellulose-silicate condensationproduct that will react with aldehyde and amine compounds to producenovel aminoplast-cellulose-silicate resins and foams. Another object isto produce alkali metal-cellulose-silicate condensation products thatwill react with aldehyde compounds and phenol compounds to produce novelphenoplast-cellulose-silicate resins and foams. Another object is toproduce alkali metal-cellulose-silicate condensation products that willreact with polyisocyanate compounds and polyurethane prepolymers toproduce novel resins and cellular product.

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail by the specificexamples which follow, it being understood that these preferredembodiments are illustrative of, but not limited to, procedures whichmay be used in the production of alkali metal-cellulose-silicatecondensation products. Parts and percentages are by weight unlessotherwise indicated.

EXAMPLE 1

About 1 part by weight of hydrated silica, 2 parts by weight of firsawdust and 2 parts by weight of sodium hydroxide flakes are mixed, thenheated to 150° C. to 220° C. while agitating at ambient pressure, withcare being taken to avoid burning the mixture, for 5 to 60 minutes oruntil the mixture softens and expands into a dark-brown, thick liquidwhich solidifies on cooling, thereby producing an alkalimetal-cellulose-silicate (sodium-cellulose-silicate) condensationproduct. The product is soluble in water, alcohols, polyhydroxylcompound and other organic solvents.

EXAMPLE 2

About 1 part by weight of silica, 1 part by weight of dry pine sawdustand 2 parts by weight of granular sodium hydroxide are mixed, thenheated to about 150° C. while agitating for about 5 minutes; the mixturebegins to expand, and on continued heating between 180° C. to 220° C., adark-brown, thick liquid, sodium-cellulose-silicate condensationproduct, is produced. The liquid solidifies on cooling. The product issoluble in water.

EXAMPLE 3

About 1 part by weight of silica sol, 2 parts by weight of white oaksawdust and 2 parts by weight of sodium hydroxide flakes are mixed, thenheated to 150° C. to 220° C. while agitating at ambient pressure for 5to 60 minutes or until all the sawdust softens and expands into a thickliquid, thereby producing sodium-cellulose-silicate condensationproduct.

EXAMPLE 4

About 2 parts by weight of fine particles of various woods listed below,2 parts by weight of potassium hydroxide and 0.5 part by weight ofsilica are mixed, then heated to 150° C. to 220° C. while agitating atambient pressure for 5 to 60 minutes, thereby producingpotassium-cellulose-silicate condensation product.

The wood is selected from the group consisting of fir, pine, redwood,cedar, oak, spruce, gum, hemlock, walnut, hickory, eucalyptus, birch,poplar, beech, maple, mahogany, aspen, ash, cypress, elm, cherry,sycamore and mixtures thereof.

EXAMPLE 5

About 3 parts by weight of sodium hydroxide flakes, 3 parts by weight ofcotton and 1 part by weight of hydrated silica are mixed, then heated to150° C. to 220° C. while agitating at ambient pressure for 5 to 60minutes, thereby producing sodium-cellulose-silicate condensationproduct.

Other celluose products may be used in place of cotton, such as woodpulp with lignin removed by soda process or by the acid sulfite process,wood pulp from waste paper and mixtures thereof.

EXAMPLE 6

About 2 parts by weight of sodium hydroxide flakes, 2 parts by weight ofdried particles of seaweed, and 1 part by weight of fine granular silicaare mixed, then heated to 150° C. to 220° C. while agitating for 5 to 60minutes, thereby producing a water-soluble mixture of sodium alginatesilicate and sodium cellulose silicate with the alginic acid stillattached to the cellulose.

Dried seaweed particles with the alginic acid extracted with an alkalicarbonate such as sodium carbonate may be used in place of seaweed(kelp).

EXAMPLE 7

About 1 part by weight of sodium hydroxide, 1 part by weight of drygranular sodium silicate and 2 parts by weight of dry particles of kelpare mixed, then heated to 150° C. to 220° C. while agitating for 5 to 60minutes at ambient pressure, thereby producing sodiumalginate-cellulose-silicate condensation product.

EXAMPLE 8

About 3 parts by weight of sodium hydroxide, 1 part by weight of driedkelp particles, 1 part by weight of fir sawdust and 1 part by weight offine granular silicoformic acid (hydrated silica containing Si-H bonds)are mixed, then heated to 150° C. to 220° C. while agitating for 5 to 60minutes, thereby producing sodium alginate-cellulose-silicatecondensation product.

EXAMPLE 9

About 3 parts by weight of dry corn cobs ground into small particlesabout the size of sawdust, 3 parts by weight of potassium hydroxidepellets and 1 part by weight of hydrated silica are mixed, then heatedto 150° C. to 220° C. while agitating for 5 to 60 minutes, therebyproducing a water-soluble, dark-brown sodium-cellulose-silicatecondensation product.

Other agricultural cellulose-containing plants may be used in place ofcorn cobs, such as corn stalks, soybean stalks, cane sugar stalks(bagasse), pea vines and stalks, bean vines and stalks, cotton stalks,rice straw, wheat straw, oat straw, barley straw, soybean stalks, sugarbeet waste, sorghum stalks, maize stalks, tobacco stalks, buckwheatstalks, etc., and mixtures thereof.

EXAMPLE 10

About 3 parts by weight of sodium hydroxide, 1 part by weight of sawdustfrom spruce wood, 1 part by weight of chopped dry seaweed, 1 part byweight of ground cotton stalks and 1 part by weight of hydrated silicaare mixed, then heated to 150° C. to 220° C. while agitating for 5 to 60minutes, thereby producing sodium alginate-cellulose-silicatecondensation product.

EXAMPLE 11

About 2 parts by weight of sodium hydroxide flakes, 2 parts by weight ofdried algae and 1 part by weight of hydrated silica are mixed, thenheated to 150° C. to 220° C. while agitating for 5 to 60 minutes,thereby producing sodium-hemicellulose-silicate condensation product.

EXAMPLE 12

About 4 parts by weight of the sodium-cellulose-silicate condensationproduct, as produced in Example 1, are added to 6 parts by weight ofwater, then filtered. About 0.1 part by weight of the weight of the woodis filtered out. To the aqueous solution of sodium-cellulose-silicatecondensation product is added hydrochloric acid until the pH is about 7;CO₂ is given off and cellulose-silicate condensation product isprecipitated out. The aqueous solution is filtered off, therebyrecovering the cellulose-silicate product. The aqueous solution isevaporated and contains salt and about 0.2 part by weight of ligninsilicate and cellulose.

EXAMPLE 13

About 3 parts by weight of sodium hydroxide flakes, 2 parts by weight ofdried ground garden plants, containing about equal parts by weight oftomato plants, bean plants, pea plants, pea vines, potato plants, grassand weeds, and 1 part by weight of silica, fine granular, are mixed,then heated to 150° C. to 220° C. while agitating for 5 to 60 minutes,thereby producing sodium-cellulose-silicate condensation product.

EXAMPLE 14

About 3 parts by weight of sodium hydroxide flakes, 1 part by weight ofpine wood sawdust, 1 part by weight of dry algae, 1 part by weight ofJohnson grass and 1 part by weight of hydrated silica are mixed, thenheated to 150° C. to 220° C. while agitating for 5 to 60 minutes,thereby producing sodium-cellulose-silicate condensation product.

EXAMPLE 15

About 4 parts by weight of the sodium-cellulose-silicate condensationproduct as produced in Example 1 are mixed with water containing 50%sodium hydrogen sulfate by weight to produce a pH of about 7. Themixture expands 3 to 4 times its original volume to produce a cellularsolid cellulose-silicate condensation product. The sodium sulfate isremoved by washing and filtering.

EXAMPLE 16

About 4 parts by weight of the sodium-cellulose-silicate, as produced inExample 2, are mixed with 8 parts by weight of water. Thesodium-cellulose-silicate aqueous solution is filtered, and very littleis not water-soluble. Dilute sulfuric is added to the aqueous solutionuntil the pH is 6 to 7; carbon dioxide evolves, and thecellulose-silicate product is precipitated. The water is filtered off,then evaporated, and about 0.25 parts by weight of thecellulose-silicate and lignin is recovered.

EXAMPLE 17

About 4 parts by weight of the sodium-cellulose-silicate condensationproduct, as produced in Example 1, are mixed with 6 parts by weight ofan aqueous solution containing 37% formaldehyde, then heated to 70° C.to 100° C. while agitating for 10 to 120 minutes, thereby producing aformaldehyde-sodium-cellulose-silicate copolymer.

EXAMPLE 18

About 4 parts by weight of the formaldehyde-sodium-cellulose-silicatecopolymer, as produced in Example 17, are mixed with phosphoric aciduntil the pH is about 6 to 7; the mixture expands 3 to 6 times itsoriginal volume, thereby producing an aldehyde-cellulose-silicatecellular solid product.

EXAMPLE 19

About 3 parts by weight of the sodium-cellulose-silicate condensationproduct, as produced in Example 3, and 2 parts by weight of furfural aremixed, then agitated at ambient temperature for 10 to 120 minutes,thereby producing an aldehyde-sodium-cellulose-silicate copolymer.

Other aldehydes may be used in place of furfural such as formaldehyde,acetaldehyde, propionaldehyde, crotonaldehyde, acrolein, butyl aldehyde,pentanals, hexanals, heptanals, octanals, and mixtures thereof.

EXAMPLE 20

To about 3 parts by weight of each of thealdehyde-sodium-cellulose-silicate copolymers produced in Example 19 isadded an acid compound, hydrochloric acid, until the pH is 6 to 7. Themixture expands 3 to 6 times its original volume, thereby producing acellular solid aldehyde-cellulose-silicate product.

Other acid compounds may be used in place of hydrochloric acid such asmineral acids, organic acids, inorganic hydrogen-containing salts andmixtures thereof.

EXAMPLE 21

2 Parts by weight of the sodium-cellulose-silicate condensation product,as produced in Example 2, 1 part by weight of urea and 3 mols of anaqueous solution containing 37% formaldehyde for each mol of urea aremixed, then agitated at a temperature between ambient temperature and100° C. for 10 minutes to 12 hours, thereby producing anaminoplast-sodium-cellulose-silicate resin.

EXAMPLE 22

To about 2 parts by weight of the aminoplast-sodium-cellulose-silicateresin, as produced in Example 21, are added a mixture of about equalmols of hydrochloric acid and phosphoric acid until the pH is 5 to 7,while vigorously agitating; the mixture expands 3 to 10 times itsoriginal volume, thereby producing a rigid cellular solidaminoplast-cellulose-silicate product.

EXAMPLE 23

2 Parts by weight of the sodium-cellular-silicate condensation product,as produced in Example 1, 1 part by weight of the sodiumalginate-cellulose-silicate, as produced in Example 7, 2 parts by weightof an amino compound, selected from the list below, and 5 mols of analdehyde for each mol of the amino compound, selected from the listbelow, are mixed, then agitated at a temperature between ambienttemperature and 100° C. for 10 minutes to 12 hours, thereby producing anaminoplast-alkali-cellulose-silicate resin.

    ______________________________________                                        Example    Amino compound Aldehyde                                            ______________________________________                                        a          urea           acetaldehyde                                        b          thiourea       propionaldehyde                                     c          melamine       crotonaldehyde                                      d          1,3-dibutylthiourea                                                                          furfural                                            e          1,3-dibutylurea                                                                              acrolein                                            f          ethylenediamine                                                                              butyl aldehyde                                      g          propylenediamine                                                                             benzaldehyde                                        h          diethylenetriamine                                                                           formaldehyde                                        i          1,3-dipropylurea                                                                             paraformaldehyde                                    j          aniline        formaldehyde                                        ______________________________________                                    

EXAMPLE 24

To about 2 parts by weight of each of the aminoplast-alkalimetal-cellulose-silicate resins, produced in Example 23, is added anacid compound, hydrochloric acid, until the pH is 6 to 7, while rapidlymixing. The mixture expands 3 to 10 times its original volume, therebyproducing cream-colored, cellular solid aminoplast-cellulose-silicateproducts.

Other acid compounds may be used in place of hydrochloric acid such asother mineral acids, organic acids, salt-producing organic compounds,inorganic hydrogen-containing salts and mixtures thereof.

EXAMPLE 25

About 2 parts by weight of an alkali metal-cellulose-silicatecondensation product listed below, 1 part by weight of a phenol compoundlisted below, and 3 mols of an aqueous solution of formaldehyde for eachmol of the phenol compound are mixed, then agitated at a temperaturebetween ambient and 100° C. for 10 minutes to 12 hours, therebyproducing a phenoplast-alkali metal-cellulose-silicate resin.

    ______________________________________                                        Example Alkali-metal-cellulose-silicate                                                                  Phenol compound                                    ______________________________________                                        a       of Example 1       phenol                                             b       of Example 2       cresol                                             c       of Example 3       creosote                                           d       of Example 4       p-cresol                                           e       of Example 5       o-cresol                                           f       of Example 6       m-cresol                                           g       of Example 7       cresylic acid                                      h       of Example 8       resorcinol                                         i       of Example 9       cashew nut shell                                                              liquid                                             j       of Example 10      Bisphenol A                                        k       of Example 11      2,6-dimethylphenol                                 l       of Example 13      p-tert-butyl phenol                                ______________________________________                                    

EXAMPLE 26

To each of the phenoplast-alkali metal-cellulose-silicate resins,produced in Example 25, is added an acid compound, phosphoric acid,until the pH is 6 to 7 while rapidly mixing. The mixture expands 3 to 12times its original volume, thereby producing a cellular solidphenoplast-cellulose-silicate product.

EXAMPLE 27

Example 25 is modified, wherein 1 part by weight of urea is added to thephenol compound, thereby producing anaminoplast-phenoplast-alkalimetal-cellulose-silicate resin; then inExample 26, a light-brown-colored, cellular solidaminoplast-phenoplast-cellulose product is produced.

EXAMPLE 28

About 2 parts by weight of the sodium-cellulose-silicate condensationproduct, as produced in Example 1, 2 parts by weight of urea, 0.5 partby weight of cresylic acid and 3 mols of an aqueous solution offormaldehyde for each mol of urea and cresylic acid are mixed at 50° C.;then 0.5 part by weight of chloroform and sufficient hydrochloric acidare added to produce a pH of 6 to 7 while rapidly mixing. The mixtureexpands 3 to 10 times its original volume, thereby producing alight-brown, rigid, tough, cellular solidaminoplast-phenoplast-cellulose product.

EXAMPLE 29

About 2 parts by weight of an alkali metal-cellulose-silicatecondensation product, as produced in Example 1, and 1 part by weight oftolylene diisocyanate are mixed, then agitated for 10 to 60 minutes at atemperature between 20° C. to 70° C., thereby producing apolyisocyanate-alkali metal-cellulose-silicate prepolymer. Then 0.4 partby weight of water containing 5% by weight of triethylamine and 10% byweight of a stabilizer (polyether polysiloxane silicate as produced bythe process of U.S. Pat. No. 4,120,937) are added to the prepolymerwhile agitating for 5 to 20 minutes or until the mixture begins toexpand. It expands 3 to 10 times its original volume, thereby producinga light-brown-colored, tough, cellular solidpolyisocyanate-cellulose-silicate product.

Other alkali metal-cellulose-silicate polymers may be used in place ofthat produced in Example 1, such as those produced in Examples 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 13 and 14 and mixtures thereof.

Other curing agents may be used in place of water containing 5% byweight of triethylamine, water containing 1% to 10% by weight of otheramine catalysts, water containing 10% to 60% by weight of a polyhydroxycompound, water containing 10% to 60% by weight of silica sol, watercontaining up to 5% by weight of an emulsifying agent, water containing10% to 50% by weight of sodium silicate, and water containing 1% to 10%by weight of an inorganic amine compound as produced by U.S. Pat. No.4,100,112.

EXAMPLE 30

About 2 parts by weight of a powdered alkali metal-cellulose-silicatecondensation product, as listed below, 2 parts by weight of a polyol,listed below, and 2 parts by weight of tolylene diisocyanate (80% of2,4-isomer and 20% of 2,6-isomer) are added simultaneously at ambienttemperature and pressure, then rapidly mixed. In a few seconds to 10minutes, the mixture expands about 8 to 12 times its original volume toproduce a rigid, tough, cream-to-brown-colored, cellular solidpolyurethane cellulose silicate product.

    ______________________________________                                        Example                                                                              Alkali metal-cellulose-silicate                                                                  Polyol                                              ______________________________________                                        a      as produced in Example 1                                                                         glycerol                                            b      as produced in Example 2                                                                         triethylene glycol                                  c      as produced in Example 3                                                                         propylene glycol                                    d      as produced in Example 4                                                                         butylene glycol                                     e      as produced in Example 5                                                                         polyethylene glycol                                                           (mol. wt. 480)                                      f      as produced in Example 6                                                                         polypropylene glycol                                                          (mol. wt. 500)                                      g      as produced in Example 7                                                                         polyethylene glycol                                                           (mol. wt. 1000)                                     h      as produced in Example 8                                                                         polyethylene glycol                                                           (mol. wt. 1500)                                     i      as produced in Example 9                                                                         polyester (3.8 mols                                                           glycerol, 2.5 mols                                                            adipic acid and 0.5                                                           mol phthalic acid)                                  j      as produced in Example 10                                                                        polyester (16 mols of                                                         adipic acid, 16 mols                                                          of diethylene glycol                                                          and 1 mol of tri-                                                             methylol propane)                                   k      as produced in Example 11                                                                        polyether (polyepi-                                                           chlorohydrin, mol.                                                            wt. 530)                                            l      as produced in Example 13                                                                        liquid hydroxyl-                                                              termin-                                                                       ated polybutadiene                                                            having 20% pendant                                                            vinyl groups (Poly                                                            B-D R45M, Arco                                                                Chemical Co.)                                       m      as produced in Example 14                                                                        liquid polysulfide                                                            polymer containing                                                            hydroxyl groups                                     n      as produced in Example 3                                                                         castor oil                                          ______________________________________                                    

EXAMPLE 31

The procedure in Example 30 is modified wherein the alkalimetal-cellulose-silicate condensation product is first mixed with thepolyol before the polyisocyanate is added.

EXAMPLE 32

About 2 parts by weight of the powdered potassium-cellulose-silicatecondensation product, as produced in Example 4, using fir wood, 2 partsby weight of powdered sodium alginate-cellulose-silicate condensationproduct, as produced in Example 10, and 4 parts by weight of anisocyanate-terminated polyurethane prepolymer, listed below, arethoroughly mixed at ambient temperature to 70° C.; then in a few secondsto about 10 minutes, the mixture begins to expand, expanding 3 to 12times its original volume to produce a tough, rigid, cellular solidpolyurethane-cellulose-silicate product.

    ______________________________________                                        Ex-                                                                           am-                                                                           ple  Isocyanate-terminated polyurethane prepolymer                            ______________________________________                                        a    toluene diisocyanate with polypropylene glycol (mol. wt.                      500) in an NCO/OH ratio or 25:1.                                         b    20% solution of a distillation residue of the distilla-                       tion of commercial tolylene diisocyanate in a crude                           phosgenation product of an aniline-formaldehyde con-                          densation with an NCO content of about 30%, with poly-                        ethylene glycol (mol. wt. 1000) to produce an isocyan-                        ate-terminated prepolymer with an NCO content of about                        17%.                                                                     c    diisocyanatodiphenylmethane with a tetrafunctional poly-                      propylene glycol (mol. wt. 500) to produce a prepoly-                         mer having about 22% NCO groups.                                         d    toluene diisocyanate with a liquid hydroxyl-terminated                        polybutadiene (mol. wt. about 1000) available from Arco                       Chemical Co. under the trade designation of "POLY B-D                         R-15M" and "POLY B-D R45M" to produce a prepolymer                            with an NCO content of about 7%.                                         e    toluene diisocyanate with castor oil to produce a prepoly-                    mer with an NCO content of about 15%.                                    f    toluene diisocyanate with a hydroxyl-group-containing poly-                   sulfide polymer to produce a prepolymer with an NCO                           content of about 12%.                                                    g    methylene bis-phenyl diisocyanate with a liquid polyepi-                      chlorohydrin to produce a prepolymer of about 16% and                         25% by weight of a resin extender, polyalpha-methyl-                          styrene are added, percentage                                                 based on weight of prepolymer.                                           h    residue of tolylene diisocyanate distillation with about                      20% by weight of NCO with polyethylene glycol (mol. wt.                       1500) to produce a prepolymer with an NCO content of                          about 11%.                                                               i    tolylene diisocyanate with a polyester (4 mols of glycerol,                   2.5 mols of adipic acid and 0.5 mol of phthalic anhy-                         dride) to produce a prepolymer with an NCO content of                         about 23%.                                                               j    tolylene diisocyanate with polyethylene (mol. wt. 2000)                       to produce a prepolymer with an NCO content of about                          28%.                                                                     ______________________________________                                    

EXAMPLE 33

About 2 parts by weight of sodium-cellulose-silicate condensationproduct, as produced in Example 2, are mixed with 2 parts by weight ofwater to produce a thick aqueous solution which is then mixed thoroughlywith 0.01 part by weight of triethyleneamine and 3 parts by weight oftolylene diisocyanate. The mixture begins to expand in 1 to 20 minutes.It expands 3 to 10 times its original volume, thereby producing a rigid,cellular solid, polyisocyanate-silicate product.

EXAMPLE 34

About 4 parts by weight of sodium-cellulose-silicate condensationproduct, as produced in Example 1, are mixed in 5 parts by weight ofwater, 0.02 part by weight of triethanolamine, 0.05 part by weight ofsodium dioctyl sulfosuccinate and 0.1 part by weight oftrichlorofluoromethane, then thoroughly mixed with an organicpolyisocyanate, listed below. The mixture expands 3 to 10 times itsoriginal volume, thereby producing a rigid, cellular solidpolyisocyanate-silicate product.

The polyisocyanates used in this Example are: tolylene-2,4- and-2,6-diisocyanate and mixtures thereof,polyphenylpolymethylene-isocyanate, diisocyanatodiphenylmethane,methylene bis phenyl diisocyanate, residue of tolylene diisocyanate withabout 20% by weight of NCO, metaphenylene, sulphonatedpolyphenylpolymethylene-polyisocyanate (sulphur content: about 1%,isocyanate content: 30%) and 20% solution of a distillation residue ofthe distillation of commercial tolylene diisocyanate indiisocyantodiphenylamine.

EXAMPLE 35

Example 32 is modified, wherein water is added to the alkalimetal-cellulose-silicate condensation product to produce an aqueoussolution containing 50% by weight of alkali metal-cellulose-silicatethereby producing polyurethane-cellulose-silicate cellular solidproducts.

EXAMPLE 36

An aqueous solution containing 60% sodium-cellulose-silicatecondensation product, as produced in Example 1, and 1% by weight oftriethylamine are mixed with an isocyanate-terminated polyurethaneprepolymer, which was produced by reacting tolylene diisocyanate withpolyethylene (mol. wt. 1000), in the ratio of 3 parts by weight of theaqueous solution to 5 parts by weight of the prepolymer. The mixtureexpands to 3 to 10 times the original volume, thereby producing a tough,rigid, cellular solid polyurethane-cellulose-silicate product.

Although specific materials and conditions were set forth in the aboveExamples, these were merely illustrative of preferred embodiments of myinvention. Various other compositions, such as the typical materialslisted above, may be used where suitable. The reactive mixtures andproducts of my invention may have other agents added thereto in order toenhance or otherwise modify the reaction and products. Othermodifications of my invention will occur to those skilled in the artupon reading my disclosure. These are intended to be included within thescope of my invention, as defined in the appended claims.

I claim:
 1. The process for the production of water-soluble alkalimetal-cellulose-silicate condensation product by the following steps:(a)mixing 3 parts by weight of a cellulose-containing plant with 1 to 2parts by weight of an oxidated silicon compound and 2 to 5 parts byweight of an alkali metal hydroxide; (b) heating the mixture at 150° C.to 220° C. while agitating for 5 to 60 minutes, thereby (c) producing awater-soluble alkali metal-cellulose-silicate condensation product. 2.The process of claim 1 wherein the alkali metal hydroxide is selectedfrom the group consisting of sodium hydroxide, potassium hydroxide andmixtures thereof.
 3. The process of claim 1 wherein the oxidated siliconcompound is selected from silica, natural silicates containing freesilicic acid radicals, sodium silicate, potassium silicate and mixturesthereof.
 4. The product produced by the process of claim
 1. 5. Theprocess of claim 1 wherein additional steps are taken wherein 1 to 5parts by weight of an aldehyde, selected from the group consisting offormaldehyde, acetaldehyde, propionic aldehyde, furfural,crotonaldehyde, acrolein, benzaldehyde, butyl aldehyde, pentanals,hexanals, heptanals, octanals and mixtures thereof, are mixed with 2parts by weight of the alkali metal-cellulose-silicate condensationproduct as produced in step (c) of claim 1, then agitated at ambienttemperature to 100° C. for 10 to 120 minutes, thereby producing analdehyde-alkali metal-cellulose-silicate copolymer; then an acidcompound, selected from the group consisting of mineral acid, organicacid, hydrogen-containing salt and mixtures thereof, is added until thepH is 6 to 7, thereby producing a cellular solidaldehyde-cellulose-silicate product.
 6. The product produced by theprocess of claim 5.